Aryl esters of bz 1-benzanthrone carboxylic acid



Patented Apr. 13, 1954 UNITED smrss PATENT OFFICE ARYL ESTEltS OF Bz l-BENZANTHRONE CARBOXYLIC'ACID James M. Straley and Raymond C. Harris, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application April 2, 1951, i Serial No. 218,912

This invention relates to new vat dye intermediates and to new vat dye compounds prepared therefrom. The invention also relates to the processes for preparing. thenewvat L dye intermediates and. the new vat'dye compounds of the invention.

I iciaims. (c1. 260-.-364) In accordance with the invention, aryl esterswl acid. Another object is to provide new valuable vat dyes which are probably l-alkoxydibenzo- (a,h) pyrene-7,l4-dionecompounds. A further object is to provide satisfactory processes for the preparation of the new compounds of the invention. Other objects will appear hereinafter.

The aryl esters of a Bz l-benzanthrone carboxylic acid of the present invention are prepared by reacting a 10methy1eneanthrone compound which is unsubstituted in at least one of the 4- and 5- positions with an-"arylacrylate. The reaction may be carried out at varying temperatures and in various solvents but the use of a nitroaryl solvent, such as nitrobenzjene, at a temperature in excess of 120 C. preferred. These compounds are also prepared by reacting a B2 1-!benzanthrone carboxylic chloride with a phenol or a naphthol in an inert solvent are temperature from about C. to about 200 C. or in an aqueous alkaline suspension at temperatures up to 100 C.

The following equations are believed-to be H- lustrative of the two reactions:

lo-methyleneanthrone Phenyl acrylata Phenyl ester of Hz l -benga ntlu'one carboxyllc acid the benzanthrone nucleus.

3 A x a, w A Bz l benzan'throne Phenol earboxylic chloride Phenyl ester of B2 l-benzanthrone carboxylic acid 10-methy1eneanthrone has the formula numbered lf'and'is numbered as indicated. IO-methyleneanthrone compounds that can be employed include, for example, IO-methyleneanthrone, 10- methylene 2- chloroanthrone. l0 methylene- 1 methylanthrone, l0 methylene 4 bromoanthrone, 10"- methylene 1 fiuoroanthrone, 10 =1methylene 3"- methylanthrone, 10 methylene-3 chloroanthrone, 10 methylene 2- methylanthrone and lfl-methylene-l-chloroanthrone.

The aryl esters of a Bz l-benzanthrone carboxylic acid of our invention contain a -COOR group, wherein R represents an aryl nucleus such .as a phenyl nucleus, a diphenyl nucleus or a.

naphthyl nucleus, joinedtothe Bz 1 position of The aryl nucleus R may be substituted with an alkyl group such as methyl or-ethyl, a halogenatom such as chlorine or bromine, a hydroxy-group or an alkoxy group such as methaoxy or ethoxy. The benzanthrone nuoleus-may-also contain substituents such as those just mentioned in connection with the member R. it o Dibenzo-(a,h) pyrene-7,14-dione has the forg 3 and is numbered as indicated. compound is also known as 3,4,8,9-dibenzopyrene-5;10- quinone.

As previously indicated, the l-hydroxydibenzo- (a,h) pyrene-'7,14-dione compounds of the invention are prepared by ring closing the ,azryl esters of a Bz l-benzanthrone carboxylic acid compound of the invention. The ring closure is effected by the action of A1018 and is facilitated I r by the incorporation of a mild oxidizing agent such as MnOz in the melt. Air or oxygen can be bubbled through the melt place of In the case of small runs the presence of air is sufiicient to promote the reaction but normally the use of a mild oxidizing agent in the melt appears to be advantageous and is preferred. The reaction will be illustrated with reference to the preparation of l-hydroxydibenzo-(a,h) pyrene- 7,14-dione which is believed to take place as follows:

table nonhydroxylated substances, Whose nature is at present unknown, are formed. These last substances are not obtained by caustic fusion of the product 7.

They need not be alkylated to prevent changes due to variations in pH.

The new l-alkoxydibenzo (a,h) pyrene-Zl idione compounds dye cotton fast shades from a cold (20 (L- C.) or a warm (30 C.-- C.) weakly-alkaline .(only a slight excess of NaOH over the theoretical amount required to form the sodium salt of the leuco dye formed by action of hydvosulfltei vat. V

The following examples illustrate the compounds of the invention and the manner in which the processes of? the invention are carried out. Parts are expressed as parts by weight.

Example 1 .60 parts of"lOmethyleneanthx-one, 51 parts of phenyl acrylate and parts of nitrobenzene 2 5 Phenyl ester of Bz l-benzanthrone (Z-hydroxybenzoyD-Bz 1- carboxyllc acid benzenthrone ably is above about 150 C. as ring closure is greatly retarded below-150 C.

The l-hydroxydibenzo-(a,h) pyrene-7,14-dione compounds of the invention are vattable and dye cotton from a vat but the dyeings change in color with changes in pH, as when the dyeing is acidified. However, when the l-hydroxydibenzo-(a,h) pyrene-7,l4-dione compounds are alkylated to convert the hydroxy group to an alkoxy group, stable vat dyes are obtained which give dyeings on cotton which do not change color with changes in 'pH.' Itjhas been further found that upon caustic fusion of either the intermediate product (5) orjthe product (6) va (n) O-alkyl 1-alkoxydlbenzo-(a,h) pyrene-7,14-dione were heated together, with stirring, at C.- 1 50 C. for 3 to 4 hours. The reaction mixture was then cooled to below 100 C. and 100 parts of methanol were added, following which the reaction mixture was cooled to about 15 C. and filtered. The reaction product, phenyl ester of B2 l-benzanthrone carboxylic acid, obtained on the filter was washed with methyl alcohol and dried. It was obtained as a yellow powder melting at 148 C.- 150 C.

By the use of 70 parts of IO-methylene-Z-chlo I roanthrone in place of lO-methyleneanthrone in the above example, a compound believed to be the phenyl ester of Bz 1-6-ohlorobenzanthrone carboxylic acid is obtained. It has the formula:

Example 2 V 62 parts of p-hydroxyphenyl acrylate, 83 parts .sodium hydroxide.

of lo-methylene anthrone and 100 parts of nitrobenzene were heated quickly to 180 C. with stirring and maintained at 180 C. to 185 C. for 1 to 2 hours while stirring. The reaction mixture was then cooled to below 100 C. and 80 parts of methyl alcohol were added, following which the reaction mixture was filtered. The reaction product obtained on the filter was washed with methyl alcohol and dried. 45 to 65 parts of the p-hydroxyphenyl esterofBz 1- benzanthrone carboxylic acid were obtained as a yellow-brown solid melting at 223 C.

By the use of 96.8 partsof 10methylene-3- chloroanthrone and 114.8parts of IO-methylene-4-bromoanthrone, respectively, in place of IO-methyIeneanthrone in the above example, the compounds believed to be the p-hydroxyphenyl ester of Bz 1-7-chlorobenzanthrone carboxylic acid andthe p-hydroxyphenyl ester of Ba l-8- bromobenzanthrone carboxylic acid, respectively, are obtained.

Emample 3 91 parts of o-chlorophenyl acrylate, 103 parts of 10-methyleneanthrone and '75 parts of nitrobenzene were heated quickly, with stirring, to 180 C. and maintained at 180 C.-185 C. for 2 hours- Some cooling was required after first reaching 180 C. as the reaction is rather exothermic. The reaction mixture was then cooled to 120 C. and '75 parts of methyl alcohol were added, following which the reaction mixture was cooled to room temperature and filtered. The reaction product obtained on the .filter was washed, with methyl alcohol and dried. 45 to 80 parts of the o-chlo'rophenyl ester of B2: 1- benzanthrone carboxylic acid were obtained as a yellowish powder, melting at 215 C.-218 C.

By the use of 110 parts of 10-methylene-1- methylanthrone and 110 parts of 10-methylen'e-.

2-methylanthrone, respectively, in place of 10- methyleneanthrone in the above example, the compounds believed tobe the o-chlorophenyl ester of Ba 1-5-methylbenzanthrone carboxylic acid and the o-chlorophenyl ester of 13 21-6- methylbenzanthrone carboxylic acid, respectively, are obtained. i

Example 4 This was. run precisely as in Example 3, using 91 parts of p-chlorophenyl acrylate instead of o-chlorophenyl acrylate. 43 to 60 parts of the p-chlorophenyl ester of Bz l-benzanthrone carboxylic acid were obtained. It melted at 230 C.

By the use of .110 parts of IO-methyIene-B- methylanthrone and 121 parts of 10-methylene- Example 301 parts of B2 l-benzanthrone carboxylic chloride and 13 parts of o-chlorophenol were heated together, with stirring, in 200 parts of o-dichlorobenzene at 130 C. for 3 to 4 hours. The o-dichlorobenzene was then removed by steam distillation and the solid product remaining was extracted on a filter with dilute aqueous The product remaining on the; filter consists of 36 parts of the og-ichlorophenyl ester of Hz l-benzanth'rone carboxylic .acid. p

Example 6 Example 7 This was run precisely as in Example 5, using 15 parts of a-naphthol in place of o-chlorophenol. parts of a product believed to be the a-naphthyl ester of Bz l-benzanthrone carboxylic acid were obtained. It melted at 235 C.-238 C.

Example 8 This was run exactly as in Example 5, using 20 parts of p-hydroxydiphenyl instead of o-chlo' rophenol. 41 parts of a product believed to be the p-phenylphenylester of Ba l-benzanthrone carboxylic acid were obtained. It melted at 195 C.-19'7 C.

Example 9 This was run exactly as in Example 1, using 54 parts of o-tolyl acrylate in place of phenyl acrylate. 51 parts of a product believed to be the o-tolyl ester of B2 l-benzanthrone carboxylic acid were obtained as a yellow powder melting at 141 C.-l42 C.

Example 10.

To a melt composed 0f,60 parts of A1013 and 20 parts of NaCl at 150 C.-160 C. there was added slowly 10 parts of the phenyl ester of Ba l-benzanthrone carboxylic acid. The reaction mixture was heated for an hour further at this temperature, after which the temperature of the reaction mixture was raised to 200 C. and held at this temperature for 4 hours. Then the reaction mixture was drowned in water and filtered. The product obtained on the filter was washed with water and, upon drying, 8.5 parts of a high melting, nonvattable product were obtained. The product is believed to be (2-hydroxybenzol) Bz l-benzanthrone.

By the use of an equivalent amount of the phenyl ester of B2 1-6-chlorobenzanthrone carboxylic acid in place of the phenyl ester of B2; l-benzanthrone carboxylic acid in the above example, (2-hydroxybenzoyD-Bz l-fi-chlorobenzanthrone is obtained.

Example 11 The (2-hydroxybenzoyD-Bz l-benzanthrone obtained as described in Example 10 was added to a melt composed of parts of A1013 and 20 parts of NaCl at 150 C.-l60 C. and '7 parts of MnOz were added. The temperature of the reaction mixture was raised to 260 C.-280 C. and maintained at this temperature for'4 to 8 hours. Upon drowning in watenfiltering and purification with sodium hypochlorite, a product was obtained which dyes cotton a brown shade from a red vat. The product thus obtained is believed to be 1-hydroxydibenzo-(a,h) pyrene 7,l4dione having the sformula numbered .6. Acidification of the dyed. fabric gave a'reddishorange dyeing. The. dyestuff. dissolves with a violet-brown color" concentrated H2804.

Theo-di- Example 12 0.5 part of cuprous chloride and 14 parts of fused potassium acetate were added to parts of 1-hydroxydibenzo-(a,h) pyrene-7,l4-dione in '75 parts of nitrobenzene. The reaction mixture was stirred and heated at 150 C. and 24 parts of methyl p-toluenesulfonate were added dropwise and the temperature held at 150 C.-16'0 C. for 3 hours. The reaction mixture was then cooled and 75 parts of methyl alcohol were added, following which the reaction mixture was filtered and the product obtained on the filter was washed first with methyl alcohol and then with hot water and dried at 110 C. 8.5 parts of a product believed to be l-metho-xydi benzo-'(a,h) pyrene-7,14-dione were obtained as a brown powder. The product is soluble in concentrated H2804 with a violet color and dyes cotton in orange-brown shades from a red vat. The dye compound obtained, as above described, has a fastness of '72 hours in the Fadeometer.

By the use of an equivalent amount of l-hydroxy-9-chloro-dibenzo-(-a,h) pyrene-7,14-dione in place of l-hydroxydibenzo-(a,h) pyrene-'l,14- dione in the above example, the vat dye compound 1 methoxy 9 chloro-dibenzo-(a,h) pyrene-7,14dione is obtained.

Example 13 parts of the p-chlorophenyl ester of Ba 1- benzanthrone carboxylic acid were added to a melt of 150 parts of A101: and parts of NaCl maintained at 140 C.-150 C. and, after the addition, the reaction mixture was held for 2 hours at this temperature. 20 parts of M1102 were added and the temperature of the I reaction mixture was raised to 200 C. and maintained at this temperature for 3 hours. After drowning in water, filtering and purification with sodium hypochlorite, there were obtained 35 parts of a product believed to be 1-hydroxy-3- chlorodibenzo-(a,h) pyrene-7,1-1-dione which is soluble in concentrated H2804 with a green color. It has the formula:

and dyes cotton a brown shade from a red vat.

Acidification of the dyed fabric gives a reddishorange shade.

Example 14 (Zr-120 C. for 10 hours, after which it was cooled slightly and parts of methyl alcohol added. The reaction mixture was filtered and the product collected on the-filter was washed first with methyl alcohol and then with hot water and dried at C. 18 parts of a product believed to be 1-methoxy-3-chloro-dibenzo-(a,h) pyrene- 7,14-dione which dyes cotton a fast orange shade from a reddish-violet vat were obtained. The fastness to light of the dyeing obtained with the dye compound of this example is apparent from the fact that it withstood 136 hours of a Fadeometer before beginning to fade. The dye dissolves in concentrated H2504 with a blue color.

Example 15 39 parts of the o-chlorophenyl ester of B2 1- benzanthrone carboxylic acid were added to a melt composed of 150 parts of AlCl3 and 50 parts of NaCl at 110 (l C. After the addition the temperature of the reaction mixture was maintained at 180 C.-l85 C. for 2 hours. Then the reaction mixture was drowned in Water, filtered, and the product obtained on the filter was washed with water to obtain 40 parts of a green powder which is apparently an aluminum complex of the desired hydroxychlorophenyl benzanthrone ketone.

Example 16 20 parts of the product of Example '15 and 10 parts of M1102 were added too. melt composed of 75 parts of A1C13 and 25 parts of NaCl at C. The temperature of the reaction mixture was then maintained at 200 C.-210 C. for 2.5 hours, following which the reaction mixture was worked up as described in Example '13. There'were thus obtained 15 parts of a product dyeing cotton a brown shade from a red-brown vat. The color of the dyeing is sensitive to changes in pH, giving an orange shade upon acidification. The dyestufi obtained dissolves in concentrated H2504 with a violet-brown color.

Example 17 A well-stirred mixture of 10 parts of the product of Example 16, 10 parts of anhydrous potassium carbonate, 20 parts of methyl p-toluene sulfonate, 0.5 part of cuprous chloride and '75 parts of nitrobenzene were heated at 150 C;- C. for 4 to 5 hours. The reaction mixture thus obtained was worked up in accordance with the procedure described in Example 12 to obtain 6 to 8 parts of a product dyeing cotton a very fast, bright orange shade from a deep red vat. The dyeing has a fastness to light of about 96 hours. The dye product dissolves in concentrated H2804 with a violet color Example 18 Emamplc 19 y 10 parts of the p-hydroxyphenylester of Bz 1- benzanthrone carboxylic acid were added to a melt composed of 75 parts of A1013 and 25 parts of NaCl at 150 C.-160 C. After 1.5 hours at this temperature, 5 parts of MnOz were added and the temperature of the reaction mixture was maintained at C.-205 C. for 3 hours. The reaction mixturewas then worked up as described in Example 17. The product thus obtained contained a considerable quantity of a nonvattable material. This nonvattable material was removed and the desired dyestufi was isolated by vatting at 60 C. in 1000 parts of water containing parts of NaOH and 15. parts of sodium hydrosulfite, filtering and blowing out the filtrate. 4 to 6 parts of a brownpowder which dyes cotton brown shades from a violet vat were thus obtained. Its color in concentrated H2804 is black. The product of this example is believed to be 1,3-dihydroxydibenzo(a,h) pyrene-7,14- dione.

Example parts of the product of Example 19 were heated for 2 hours with 75 parts of nitrobenzene, 14 parts of potassium carbonate, 0.5 part of cuprous chloride and 50 parts of methyl ptolu-enesulfonateat 145 C.-150? C. The reaction mixture was worked up in accordance with the procedure described in Example 16 to obtain 15 parts of a product dyeing cotton violet shades from a green vat. The dyeing obtained had a light fastness of about 72 hours. The vat dye compound obtained is believed to be 1. -dimethoxy-dibenzo-(a,h) pyrene-M-dione.

Example 21 parts of the o-tolyl ester of Bz l-benzanthrone carboxylic acid were added to a melt of 150 parts of AlCls and 50 parts of NaCl at 140 C.- 150 C. and after the addition the reaction mixture was maintained for a hours at this temperature. 20 parts of mo: (80%) were added and the temperature of the reaction mixture was raised to 200" C. and maintained at this temperature for 3 hours. The reaction mixture was then drowned in water, filtered and purified by treatment with sodium hypochlorite. 32 parts of a product dyeing cotton in brown shades from a red vat were obtained. The dyestufi thus obtained dissolved in concentrated H2804 with a violet-brown color. 1

Example 22 Example 23 10 parts of the product of Example 12 were added at 120 C.-130 C. to a melt composed of 50 parts of KOH and 25parts of ethyl alcohol. The temperature of the reaction mixture was brought to 145 C. and held at 145 C.-l50 C. for 3 hours. The melt was then cooled and drowned in water and air-blown until complete precipitation of the dye product was effected. The reaction mixture was then filtered and the product obtained on the filter was washed with water and dried. 8 parts of a vattable dye product soluble in concentrated H2804 with a bright blue color and dyeing cotton fast brown shades from a red-violet vat were obtained. The dyeings thus obtained were unaffected by changes in pH and had a fastness to light of about 2 hours.

Example 24 10 parts of the product of Example 19 were added at 120 C.-130 C. to a melt composed of 50 parts of KOH and 25 parts of ethyl alcohol. The temperature of the reaction mixture was Example 25 V 10 parts of the product of Example 13 were added at a temperature of C.- C. to a melt composed or 50 parts of KOH and 25 parts of ethyl alcohol. The temperature of the reaction mixture was brought to C. and held at 145 C.-l50 C. for 3 hours. The cooled melt was drowned in water and air-blown until complete precipitation of the desired dye product was effected. The reaction mixture was then filtered and the product obtained on the nlter was washed with water and dried. 3.5 parts oi a product soluble in concentrated HsSua with a blue color and dyeing cotton violet snaoesrrom a red vat were obtained. The dyemgs'had a lastmess to light of about 84 hours and were unaffected by changes in pH.

The iusion reactions, such as those described in Examples 23, as and 20, may be perrormed at temperatures of from about 100 C. to about 200 (3., but that in the range of about 140 0-100 C. the fusion is complete in ashorter time than when a lower temperature isused. Although a temperature as high as about 200 C. can be employed, there seems to be little, if any, advantage in using a temperature above C. and, accordingly, the use of temperatures in the range of about 140 C.-1 50 C. is preferred.

By light fastness is meant the number of hours a dyeing can be exposed in a Fadeometer before it begins to fade. Thus, a light fastness of about 72 hours means that the dyeing can be exposed for about 72 hours in the Fadeometer before fading occurs.

The phenyl acrylate compounds used in the preparation of the aryl esters of a benzathrohe carboxylic acid compounds of the invention are prepared by reacting acrylyl chloride with an alkali metal salt of a phenol which may be substituted, for example, with a hydroxy group, an alkyl group such as methyl or ethyl, a halogen atom such as chlorine or bromine or an alkoxy group such as methoxy or ethoxy. Although various techniques for the reaction can be employed, it is preferred to react acrylyl chloride with the sodium salt of the phenol in the presence of an inert diluent such as benzene, toluene or chlorobenzene. The sodium salt of the phenol is conveniently prepared by reacting the phenol with sodium methoxide. The following examples illustrate the manner of preparation of the phenyl acrylate compounds.

Example 26 V boxylic acid.

11 refluxed for 3 hours and filtered'while hot. The filtrate was concentrated invacuo to incipient crystallization and cooled strongly. After filtration and drying, there were obtained 61 parts of p-hydroxyphenyl acrylate melting'at 78 C. Its solution in CC14- adds bromine without evolution ofHBr. 7 Example 27 128.5 parts of ochlomphenol. 54 parts of sodium methoxide, 650 parts of toluene and 90 parts of acrylyl chloride werereacted together in accorda ce with the procedu e descr b d n ample 1 .2 parts of oreblo p e acrylate boil n t 9 ,Q/ mm N11 =l5330 were ob: aine Its olut on CCli a s bremine w out imi at n oi H13 Ewample 28 By the use of 128.5 parts of p-chlorophenol in p ace oi e-ehlolronhene n Example 7, 131 pa ts f p-ehlorophemrl e ylate. b i n at. 96 c. 98C ./5 rum. N 5 1 .5425 were obtained. Its soqn n C i adds bromine wi hout el m nat of HBr.

We claim:

'1. A compound having the general formula:

wherein X represents a member selected from the group consisting of a hydrogen atom, a chlorine atom, a hydroxy' group and a methyl group,

2. The phenyl esterof Bz -1-benzanthrone car- 3. The p-hydroxyphenyl ester of Bz l-benzanthrone carboxy-lio acid. 1

4. The p ohlorophenyl ester of Ba l-benzanthrone oarboxylic acid.

12 '5. The o-chlorophenyl ester of Bz l-benzan throne carboxylic acid. r

r 6. The a-naphthyl ester of B2 l-benzanthrone carboxylic acid. a r

7. A compound having the general formula:

@COOQ wherein Q represents a member selected from the group consisting of an unsubstituted diphenyl nucleus, an unsubstituted naphthyl nucleus and References Ci ed. n the file of this patent UNITED STATES PATENTS Number Name Date 1,693,447 Kranzlein et a1. Nov. 27, 1928 FOREIGN PATENTS Number Country Date 597,325 Germany May 1932 OTHER REFERENCES Houben, Das Anthraoen und die Anthrachinone, page 572 (1929), George Thieme, Verlag Leipzig.

Elseviers Encyclopedia of Ortanic Chemistry, vol. 13, Series-111, page 373 (1940) 

4. THE P-CHLOROPHENYL ESTER OF BZ 1-BENZANTHRONE CARBOXYLIC ACID. 